Machine Translated by Google

International Journal of Eco-Innovation in Science and Engineering Vol. 01 (2), 2020

(30-35) https://ijeise.upnjatim.ac.id/ E-ISSN: 2721-8775

Articles

Recovery of Phosphate and Ammonium from Dairy Cow

Urine by Struvite Crystallization with Vertical Reactor
Luluk Edahwati1,a,* , Sutiyono1, Rizqi Rendri Anggriawan1, b

1Department of Chemical Engineering, Faculty of Engineering, UPN "Veteran" East Java

Jl. Rungkut Madya No.1, Mt. Anyar, District. Mt. Anyar, Surabaya, Indonesia

E-mail: a,*lulukedahwati@gmail.com, brrendrianggriawan24@gmail.com

Received: 12th October 2020; Revised: 27th October 2020; Accepted: 30th November 2020; Available
online: 1th December 2020; Published regularly: October 2020.

Abstract

Excess phosphate (PO4 3-) and ammonium (NH4 +) in wastewater can cause environmental damage, such as pollutants
and eutrophication in water. Dairy cow urine is a dangerous liquid waste that contains high amounts of phosphate and
ammonium. The removal of PO4 and NH4 components can be done by crystallizing them into struvite fertilizers. Struvite
(MgNH4PO4.6H2O) is a mineral formed from magnesium, ammonium, and phosphate with the equimolar ratio. The
crystallization process of struvite is carried out using a vertical reactor. MAP solution (magnesium ammonium
phosphate) is prepared by reacting MgCl2, H3PO4, and dairy cow urine with MAP molar ratio of 1 : 1 : 1 and KOH 1N.
The study ran in pH 8; 8.5; 9; 9.5; 10 and temperature variations of 25, 30, 35, 40, 45ÿC in vertical reactor continuously.
The struvite precipitate was filtered and dried, it was analyzed by XRF to determine the struvite composition and SEM
to determine the morphology of the struvite. The results showed that the best percentage of phosphate and ammonium
was at 45ÿC and pH 9.5, it was 33.2% and 27.9%.

Keywords: ammonium, phosphate, recovery, struvite, vertical reactors.

1.Introduction minerals, lactose, enzymes, hormones and acids.

The presence of high amounts of phosphate
(PO4 3-) and ammonium (NH4 +) compounds in
wastewater causes serious environmental causes
problems. Ammonium excess is a very dangerous
pollutant because it can cause the death of organisms
[1]. While the excess of P (phosphorus) or phosphate
components causes eutrophication where there is an
uncontrolled increase in aquatic plants causing damage
to the aquatic system [2]. One example of waste that
contains high concentrations of phosphate and
ammonium is dairy cow urine [3]. Dairy cow urine is the
residual liquid from feed that has been digested and
metabolized by the cow's body. Cow urine contains
nitrogen, sulfur, phosphate, ammonium, sodium,
manganese, iron, silica, chlorine, magnesium, calcium,
The composition of cow urine is almost the same as
human urine [4]. From its nutritional aspect, cow urine
has a higher nutrient content compared to its solid feces
[5]. Ammonium and phosphate content is large enough
to make cow urine can be used as struvite fertilizer.
Struvite is a mineral formed from magnesium,
ammonium, and phosphate with the equimolar ratio. The
molecular formula of struvite is MgNH4PO4.6H2O
(magnesium ammonium phosphate hexahydrate).
Struvite has morphology like orthorhombic crystal.
Struvite is a white crystal, it can be shaped like a plate,
but the shape can be either round or dendrite.
Struvite dissolves slowly in neutral water. The ability of
slow release struvite is used to substitute urea fertilizer
which has side effects on
deteriorating soil quality. Struvite crystals can

DOI:10.4186/ijeise.upnjatim.ac.id/E-ISSN: 2721-8775
30
Machine Translated by Google

International Journal of Eco-Innovation in Science and Engineering Vol 01 (2), 2020

form if concentrations of magnesium, ammonium, and

phosphate in solution exceed the solubility product (Ksp).
Struvite formation reaction [6] :

Mg 2+ + NH4 + + PO4 3- + 6H2O ÿ MgNH4PO4 .6H2O (1)

This crystallization can convert MAP solutions into

struvite crystals and be used as fertilizer for plants.
Struvite crystals formation through nucleation first. The
crystal core will grow larger until it reaches a stable size.
The process of making struvite by crystallization is a raw
material in the form of waste containing one of the struvite-
forming elements that is collected before being reacted.
Then the waste is mixed with reactants containing other
struvite-forming elements, flowed into the crystallization
reactor.

After mixing into a solution in the crystallization reactor

in the flow of the aeration process, a struvite crystal will
settle under the crystallization reactor section [7]. pH is
an important factor in the formation of struvite and the
process of crystallization. An increase in pH causes more
deposition to form due to strong and perfect ionic bonds Fig. 1. Vertical Reactor
because the activity of the NH3 and PO4 ions is influenced
by pH. The increase of pH in solution is directly Information: a.
proportional to the removal of ammonium and phosphate MAP Storage Tank b. KOH
[8]. The addition of excess magnesium can increase Storage Tank c. MAP valve
removal efficiency in this process, but can also reduce d. KOH valve e.

the purity of struvite formed [9]. In addition, the aeration Reactor Column f.
Thermocontrol g.
process is used to release or dissolve ammonium from
Struvite Overflow
solution. The air
Solution Storage Tank h. Water Storage Tanks i.
Water Pump j. Rotarometer
k. Struvite Crystals
flow dilutes the NH4-N gas phase concentration and
Tank l. Reactor
increases the driving force to dissolve NH4-
Jacket m. MAP Solution
N to separate the gas phase [10]. The crystallization
Storage Tanks
process using a stirred reactor is also not profitable
because the struvite crystals formed will adhere to and
stick to the stirrer so
Dairy cow urine contains high amounts of ammonium
that the resulting product can be reduced. In addition, so it can be used as ammonium
adhering to the product on the mixer can inhibit the
source. Magnesium chloride (MgCl2) as magnesium
movement of the mixer so that
source, phosphoric acid (H3PO4) as phosphate source,
the mixer rotates more slowly. Research on the formation
and potassium hydroxide (KOH) solution are used as a
of struvite using an aeration process can remove a
pH controller.
maximum of 83.7% of phosphate [7].
A vertical reactor shown in Figure 1 is used for the
crystallization process of struvite formation. The reactor

2. Materials and Methods is approved with volume 498.75 mL, height 50 cm with
outer diameter 5 cm; inner diameter 2.5 cm. In this reactor,
water is

DOI:10.4186/ijeise.upnjatim.ac.id/E-ISSN: 2721-8775
31
 . . . . .
Machine Translated by Google NH4 17.6 21.7 21.0 22.8 22
9 PO4 22.7 24.3 25.2 28.3 26
NH4 20.8 22.0 24.1 26.9 24
International Journal of Eco-Innovation in Science9.5 23.5
PO4 Vol 01 (2),
and Engineering 25.8 28.9 33.2 30
2020
NH4 22.4 24.7 27.4 24.4 27
10 PO4 21.3 21.8 23.3 24.0 24
used as a stirrer on the flow that is in the vertical NH4 20.7 23.6 22.6 23.1 22
reactor, so that the MAP solution (Magnesium
Ammonium Phosphate) that is in the reactor can be 3.1. The Effect of Temperature on Phosphate and
homogeneous. Ammonium Content
MAP solution (Magnesium Ammonium Phosphate)
35
is made by comparing the concentration ratios Mg: NH4:
PO4 = 1: 1: 1 and KOH concentration of 1N. The reactor 30
is filled
25
with ¾ the reactor volume. Turn on the
compressor to drain the air into the reactor. 20
After the process was steady state, the struvite
15

Component
Phosphate
(%)
precipitate was filtered and dried. Record the weight
and analyze using XRF and SEM. 10

3. Results and Discussion 5

0
Dairy cow urine is taken from a farm in
25 30 35 40 45
Pasuruan, East Java. Cow urine has yellow to light
Temperature (ÿC)
brown color with a non-pungent odor. The results pH 8 pH 8.5 pH 9 pH 9.5 pH 10
of the urine analysis are as follows:

Fig. 2. Effect of temperature (ÿC) on phosphate content

Table 1. Dairy Cow Urine Analysis Results Parameters (%) in various pH
Units Test Results
Magnesium (Mg) mg/kg 170.57 Temperature can affect the solubility and
Ammonium (NH4) mg/kg Dairy 430 morphology of struvite. High temperatures in
cow urine is taken from a farm in Phosphate
(PO4) mg/kg Pasuruan, East 100 crystallization usually cause controlled diffusion
Java. Cow urine has yellow to light brown color
growth, while low temperatures cause integrated
with a non-pungent odor. The results of the urine
surface growth. In addition the growth rate of
analysis are as follows: often increases and can affect
crystallization at high temperatures
the size and shape of the crystals [11].

It is known that the phosphate content in
wastewater that exceeds quality standards can
result in eutrophication. Eutrophication is an
environmental problem caused by waste [11].
Besides that in the dairy cow urine, there is
ammonium content if just dumped into the
environment causing hazardous and damage.
In the graph shown by Figure 2, it can be
explained that the percentage phosphate component
for pH 8; 8.5; 9; 9.5; and 10 tends to increase at the
temperature of 40ÿC and has decreased at the
temperature of 45ÿC. It has been because the
solubility product (Ksp) increases at high
temperature. Most studies usually used a process
temperature from 25 to 35ÿC [12]. In addition,
phosphorus removal efficiency increased from 63%
to 78% when temperature increased from 5 to 50°C
[13]. Its in line with this study, where at temperatures
of 25 to 40ÿC resulting in an increase in the
efficiency of phosphate removal. Whereas at
temperature of 45ÿC there is a decrease in phosphate
removal.

DOI:10.4186/ijeise.upnjatim.ac.id/E-ISSN: 2721-8775
32
Machine Translated by Google

International Journal of Eco-Innovation in Science and Engineering Vol 01 (2), 2020

dominate the crystal growth of

struvite, ultimately resulting in smaller crystals [16].
35

30
35

25
30

20
25

15
Component
Ammonium

20
(%)

10
15

Component
Phosphate
(%)
5
10

0
5
25 30 35 40 45
0
Temperature (°C)
pH 8 pH 8.5 pH 9 pH 9.5 pH 10 8 8.5 T = 9 9.5 10
25ÿCT = 30ÿCT = 35ÿC
pH
Fig. 3. Effect of temperature (ÿC) on ammonium T = 40ÿCT = 45ÿC

content (%) in various pH

Fig. 4. Effect of pH on phosphate content (%)
Ammonium components are presented in Figure 3. in various temperatures (ÿC)
With increasing temperature from 25 to 40°C, the
30
percentage of ammonium increases to a peak at 40ÿC
then decreases at 45ÿC. This is in line with the 25
temperature recommendations in the formation of
struvite and ammonium removal. The recommended 20
temperature for removing ammonia from struvite is
15
between 25 and 40°C. Because the heating of struvite
was carried out in the sealed condition, most of the
10
Component
Ammonium

ammonia was possibly changed into NH3 species at

these high temperatures [14]. 5
(%)

0
3.2. The Effect of pH on Phosphate and 8 8.5 T = 9
25ÿCT = 30ÿCT = 35ÿC
9.5 10
Ammonium Content
pH
T = 40ÿCT = 45ÿC

pH is an important factor in the formation

of struvite and the process of crystallization. Fig. 5. Effect of pH on ammonium content
Struvite precipitation potential significantly increases (%) in various temperatures (ÿC)
due to its solubility and decreases with the increase of
pH. Increase in pH produces higher nuclei population 3.3. Morphologies of Struvite from Diary
densities which might be the cause of producing smaller Cow Urine
crystals. The struvite content decreases to around <
30-70% Morphological characteristics of struvite
at over pH 9.5 [15]. were observed by scanning electron microscopy
Both of percentage ammonium and (SEM). SEM draws the surface of struvite so
phosphate component in struvite, indicating that the morphological form of struvite can be
that the higher of pH value occurs an increase enlarged resolution [15]. The results of
of the percentage component. Meanwhile, observations using SEM at pH 9 are shown in
the peak of crystal growth in this study was Figure 6 at 700x magnification.
at pH 9.5 and began to decline at pH 10 as
presented in Figure 4 and Figure 5. At pH 10, the crystal nucleation may

DOI:10.4186/ijeise.upnjatim.ac.id/E-ISSN: 2721-8775
33
Machine Translated by Google
International Journal of Eco-Innovation in Science and Engineering Vol 01 (2), 2020
Fig. 6. SEM analysis results of struvite at pH 9
In theory, it is stated that struvite has a
shape like an orthorhombic crystal or rod shape
[10]. In this observation, the morphological
shape of struvite is rod shape with a part of the
rod line that is not sharp. But there is a few
struvite in Figure 6 has irregular shape which
means the struvite obtained an impurity or other
mineral formed during the crystallization [10].
4. Conclusions
The best percentage of phosphate and
ammonium components in the struvite
crystallization from dairy cow urine was obtained
at temperature of 45°C and pH of 9.5, that was
33.2% phosphate and 27.9% ammonium.
Acknowledgment
The authors wish to express our gratitude to
University of National Development "Veteran"
East Java to support this research
programs.
References
[1] HA Aka, Suhendrayatna, and Syaubari, "Reducing
Ammonia Levels in Liquid Waste by the Water
Plant Typha Latifolia (Torch Plant)," J. Disaster
Science, vol. 4, no. 3, pp. 72–75, 2017.
[2] B. Liu, A. Giannis, J. Zhang, V. W. Chang,
and J. Wang, “Chemosphere
DOI:10.4186/ijeise.upnjatim.ac.id/E-ISSN: 2721-8775
Characterization of induced struvite
formation from source-separated urine
using seawater and brine as magnesium
sources,” Chemosphere, vol. 93, no. 11, pp.
2738–2747, 2013.
[3] CW Purnomo, NP Kusumawardhani, and YN
Marpaung, "Phosphate recovery from dairy
urine by struvite crystallization Phosphate
Recovery From Dairy Urine By Struvite
Crystallization," in The 3rd International
Seminar on Chemistry, 2018.
[4] H. Gulhane, A. Nakanekar, N. Mahakal, S.
Bhople, and A. Salunke, “Gomutra (Cow
Urine): a Multidimensional Drug Review
Article,” Int. J. Res. Ayurveda Pharm., vol. 8,
no. 5, pp. 1–6, 2017.
[5] VN Sari, M. Same, and Y. Parapasan, "The
Effect of Concentration and Fermentation
Time of Cow Urine as Liquid Fertilizer on
the Growth of Rubber Seedlings (Hevea
brasiliensis Muell. Arg.)," J. Agro Ind.
Perkeb., vol. 5, no. 1, p. 57, 2017.
[6] MI Ali and Rajshahi, Struvite crystallization
from nutrient rich wastewater., no. July. 2005.
[7] E. Ariyanto, A. Melani, and T. Anggraini,
"Removal of PO4 in Hospital Wastewater
for Struvite Fertilizer Production,"
Jurnal.Ftumj, pp. 1–8, 2015.
[8] Iswahyudi, LK Muharrami, and Supriyanto, "Processing
Salt Waste (Bittern) into Struvite by Controlling
pH," in National Seminar: Initiating the Revival of Local
Agricultural and Marine Leading Commodities, Faculty
of Agriculture
Trunojoyo Madura University, 2013, pp. 708–
715.
[9] WP and IW Iswarani, "Recovery of Phosphate
and Ammonium Using Struvite Precipitation
Techniques," J. Tek. ITS, vol. 7, no. 1, pp.
7–9, 2018.
[10] L. Edahwati, Sutiyono, N. Zahra, and H.
Septiani, "Magnesium Recovery of Struvite Formation
Based on Waste Salts (Bittern) with a Bulkhead
Reactor," Int. J. Eco-Innovation Sci. Eng., vol. 1, no.
01, pp. 1–5, 2020.
[11] Sutiyono, Luluk edahwati, K. Pratiwi, and A.
Fanani, "Tofu Factory Liquid Waste for
Making Struvite with Canted Vertical
Reactors," Int. J. Eco-Innovation Sci. Eng.,
vol. 1, no. 01, pp. 13–17, 2020.
[12] D. Crutchik and J.M. Garrido, “Kinetics of
34
Machine Translated by Google

International Journal of Eco-Innovation in Science and Engineering Vol 01 (2), 2020

the reversible reaction of struvite

crystallization,” Chemosphere, vol. 154, pp. 567–
572, 2016.
[13] SH Lee, BH Yoo, SJ Lim, TH Kim, SK Kim, and JY
Kim, “Development and validation of an equilibrium
model for struvite formation with calcium co-

precipitation,” J. Cryst. Growth, vol. 372, pp. 129–

137, 2013.
[14] AP Bayuseno and WW Schmahl, “Thermal
decomposition of struvite in qualitative and
water: quantitative mineralogy analysis,”
Environ. Technol. (United Kingdom), vol. 0, no. 0, pp.
1–7, 2019.
[15] MM Rahman, MAM Salleh, U. Rashid, A. Ahsan, MM
Hossain, and CS Ra, “Production of slow release
crystal fertilizer from wastewaters through struvite
crystallization - A review,” Arabic. J. Chem., vol. 7,
no. 1, pp. 139–155, 2014.

[16] K. Suzuki et al., “Removal and recovery of

phosphorous from swine wastewater by
demonstration crystallization reactor and struvite
accumulation device,” Bioresour.
Technol., vol. 98, no. 8, pp. 1573–1578, 2007.

DOI:10.4186/ijeise.upnjatim.ac.id/E-ISSN: 2721-8775
35